JP2019119616A - Roll-state wound body of silicon oxide thin film laminate, and manufacturing method thereof - Google Patents

Abstract

To provide a roll-state wound body of a silicon oxide thin film laminate formed by laminating a porous silicon oxide thin film on the surface of a plastic substrate.SOLUTION: There is provided a roll-state wound body of a silicon oxide thin film laminate comprising a substrate film, and a silicon oxide thin film formed on its surface. In the roll-state wound body of the silicon oxide thin film laminate, a porosity of the silicon oxide thin film is 10% or more as a value calculated from a relational expression between the porosity and a refraction index by the Lorentz-Lorenz equation.SELECTED DRAWING: None

Description

  The present invention relates to a roll of silicon oxide thin film laminate and a method of manufacturing the same.

As a method of forming a silicon oxide thin film, a sol liquid containing an inorganic compound of at least one element selected from the group consisting of silicon, aluminum, zirconium and hafnium, which is formed by a sol-gel method, is coated on a substrate There is known a method of forming a silicon oxide thin film in which ultraviolet rays of at most 100 mJ / cm ² are irradiated while being heat-treated to a temperature not exceeding 200 ° C. (Patent Document 1).

JP 2002-187738 A

  By the way, when the above-mentioned method in which the heating step is essential is applied to a plastic substrate, it is difficult to avoid deterioration of the substrate and to obtain a high precision optical member such as an antireflection film. In addition, in consideration of the difficulty of uniform heat treatment, it can not cope with large area film formation, and moreover, film formation is difficult for a short time, so that there is a problem of poor productivity.

  Also, although a large area silicon oxide thin film laminate is desired to be in the form of a roll wound body from the viewpoint of productivity and handleability, a roll wound body of an excellent antireflective film still appears due to the following reasons I did not.

  That is, the anti-reflection function depends on the refractive index, and is enhanced as the refractive index is lower, and according to the relationship of porosity and refractive index by Lorentz-Lorentz, the material's refraction makes the material refractive. In general, the adhesion between the substrate film and the silicon oxide thin film formed on the surface is lowered by making the film porous, and the form of a roll-shaped wound body is to be taken. Is difficult.

  This invention is made in view of the said situation, The objective is to provide the roll-shaped winding body of the silicon oxide thin film laminated body which laminated | stacked the porous silicon oxide thin film on the surface of the plastic base material. And the other object of the present invention does not require a heating process, therefore, it can be applied to an optical member with high accuracy, and further, roll-like winding of a silicon oxide thin film laminate capable of forming a large area and a short time. It is to provide a method for continuous production of the body.

  The present inventors skillfully utilize a hydrolyzable silane compound in a sol-gel method in order to achieve the above-mentioned problems, and if ultraviolet irradiation is performed under specific conditions, the plastic substrate is not necessarily required in the heating step. We have obtained the knowledge that a porous silicon oxide thin film can be formed as a high adhesion layer on the surface of

  The present invention has been completed based on the above findings, and the first summary thereof is a roll-like wound body of a silicon oxide thin film laminate comprising a base film and a silicon oxide thin film formed on the surface thereof. And wherein the porosity of the silicon oxide thin film is 10% or more as a value calculated by the relational expression of the porosity and the refractive index according to the Lorentz-Lorentz equation. Exist in the body.

  And the 2nd summary of the present invention prepares the coating liquid for silicon oxide thin film formation containing the binder liquid consisting of the reaction composition obtained by making a hydrolyzable silane compound hydrolyze and carry out condensation reaction, and a silica particle. And coating the coating liquid for forming a silicon oxide thin film on the surface while pulling out the rolled plastic substrate, and drying the coating film on the surface of the plastic substrate carried out from the first step. Second step, the coating film on the surface of the plastic substrate carried out from the second step is irradiated with ultraviolet rays to be cured to form a silicon oxide thin film, and the silicon oxide thin film laminate carried out from the third step In a method for continuously producing a roll-like wound body of a silicon oxide thin film laminate, comprising the fourth step of winding and winding the film into a roll. To.

  According to the present invention, the above object is achieved.

Detailed process schematic drawing for carrying out the continuous manufacturing method of the present invention

  BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below, but for the convenience of explanation, first, a method for continuously producing a roll of silicon oxide thin film laminate will be described.

<Continuous production method of roll-like wound body of silicon oxide thin film laminate>
In the present invention, a coating liquid for forming a silicon oxide thin film is prepared, which contains a binder liquid comprising a reaction composition obtained by hydrolyzing and condensing a hydrolyzable silane compound, and silica fine particles.

[Binder solution]
The binder liquid comprises a reaction composition obtained by hydrolyzing and condensing a hydrolyzable silane compound.

  The binder acts between the silica particles to form a silicon oxide thin film and has the function of adhering the silicon oxide thin film to the surface of the substrate, and the function is the property of the reaction composition obtained by the difference in the preparation method The ideal binder is a reaction composition rich in a linear structure with a large amount of -OH groups. And if such an ideal binder is used, the adhesiveness of the silicon oxide thin film with respect to a base material can be improved notably.

  In the preparation of the binder solution, a hydrolyzable silane compound is used which is composed of a bifunctional hydrolyzable silane compound and at least 50% by weight of which is a multimer, in the absence of silica particles. The above reaction is preferably carried out by continuously dropping an aqueous acid catalyst solution into the dissolved hydrophilic solvent solution under stirring conditions.

  The hydrolyzable silane compound is a silane compound having a hydrolysable group such as an alkoxy group, an alkoxyalkoxy group, an acyloxy group, an aryloxy group, an aminoxy group, an amido group, a ketoxime group, an isocyanate group or a halogen atom.

  Among the above, alkoxysilane compounds are preferably used. Examples of the alkyl group of the alkoxy group (-OR) include lower alkyl groups such as methyl, ethyl, propyl and butyl. Depending on the number of hydrolyzable groups, one having 1 to 4 functions is known.

  Representative examples of alkoxysilane compounds include dimethyldimethoxysilane (DMDMS), methyltrimethoxysilane (MTMS), tetramethoxysilane (TMOS), dimethyldiethoxysilane (DMDES), methyltriethoxysilane (MTES), tetraethoxysilane (TEOS) etc. are mentioned.

  The multimer of the hydrolyzable silane compound is obtained by polymerizing (oligomerizing) the above monomers by condensation. In this reaction, first, a silanol group (-Si-OH) is formed by hydrolysis of an alkoxy group. At the same time, alcohol (R-OH) is formed. Next, siloxane bonds (-Si-O-Si-O-) are formed by (dehydration) condensation of silanol groups, and this condensation is repeated to form a siloxane oligomer. As the multimer of the alkoxysilane compound, a multimer of tetramethoxysilane in which R is a methyl group or a multimer of tetraethoxysilane in which R is an ethyl group is preferable from the viewpoint of hydrolyzability and condensation of an alkoxy group. .

The structure of the multimer includes linear, branched, cyclic, and network structures, and when a multimer of tetraalkoxysilane is shown as having a linear structure, it is represented by the following general formula .
[Chemical formula 1]
RO (Si (OR) ₂ O) n R (I)

  In the general formula, n represents the degree of multimerization. Usually available multimers are compositions of n different multimers and thus have a molecular weight distribution. The degree of multimerization is represented by n averaged.

The degree of multimerization of a tetrafunctional hydrolyzable silane compound such as tetraalkoxysilane or a multimer thereof may also be represented by "silica fraction". "Silica component" is a mass ratio of silica (SiO ² ) generated from the compound, and can be obtained by stably hydrolyzing the compound and measuring the amount of silica generated by calcination. In addition, “silica content” also indicates the ratio of silica generated to one molecule of the compound, and is a value calculated by the following formula.
[Equation 1]
Silica content (parts by mass) = degree of multimerization × molecular weight of SiO ₂ / molecular weight of the compound

  The degree of multimerization n is usually 2 to 100, preferably 2 to 70, and more preferably 2 to 50. Such multimers are already commercially available and are convenient to use. As the degree of multimerization n increases, the molecular weight of the produced binder increases and the molecular weight distribution becomes broader, so a multimer having a degree of multimerization n of more than 100 is inappropriate.

  As commercial products of multimers of hydrolyzable silane compounds, MKC Silicate MS 51, MKC Silicate MS 56, MKC Silicate MS 57, MKC Silicate MS 56 S (all are tetramethoxysilane multimers) manufactured by Mitsubishi Chemical Corp., and Methyl manufactured by Colcoat, Inc. Examples thereof include silicate 51 (multimer of tetramethoxysilane), methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, ethyl silicate 40 manufactured by Tama Chemical Co., Ltd., silicate 45 (all are polymers of tetraethoxysilane), and the like.

  The polymer ratio in the bifunctional hydrolyzable silane compound is preferably 70% by weight or more. When the amount of the multimer used is small, the hydrolysis and condensation reactions to which the monomer is subjected decrease the OH group and increase the branched, cyclic and network structure in the reaction composition.

  The hydrolysis and condensation reactions are sequentially performed, and when silica particles are present in the reaction process (by heating), each component generated during the reaction is adsorbed on the surface of the silica particles. This adsorption is a strong state in which the binder component OH group and the silica particle OH group form a hydrogen bond or a siloxane bond, and the OH group contributing to the base material adhesiveness of the binder and the increase in the strength of the silicon oxide thin film It will decrease. In addition, the binder component adsorbed to the silica particles serves as a crosslinking point to increase the branched structure and the network structure. On the other hand, the reaction product prepared in the absence of silica particles is rich in the linear structure having a large amount of OH groups. Therefore, a binder liquid is prepared in the absence of silica particles, and the obtained binder liquid and the silica fine particles are mixed at room temperature to prepare a coating liquid for forming a silicon oxide thin film.

  The above reaction is carried out by continuously dropping an aqueous acid catalyst solution under stirring conditions into a hydrophilic solvent solution in which a hydrolyzable silane compound is dissolved.

  The hydrophilic solvent is not particularly limited as long as it can dissolve the multimer of the hydrolyzable silane compound, but generally, alcohols such as methanol, ethanol, propanol and butanol, ethyl cellosolve, butyl cellosolve and propyl cellosolve Cellosolves such as ethylene glycol, propylene glycol, glycols such as hexylene glycol are used.

  The amount of the hydrophilic solvent used is not particularly limited, but in view of the coatability of the coating liquid for forming a silicon oxide thin film prepared by mixing the silica fine particles with the binder liquid, the ratio to 100 parts by weight of the hydrolyzable silane compound The amount is usually 0.1 to 100 times by weight, preferably 1 to 10 times by weight. Incidentally, the multimer of the hydrolyzable silane compound is a composition comprising the components having different degrees of multimerization as described above, and the viscosity becomes higher as the degree of polymerization becomes higher. On the other hand, the commercially available product of that monomer, for example, dimethyldimethoxysilane, is usually a 99% by weight pure solution.

  The acid concentration in the aqueous acid catalyst solution is usually in the range of 0.1 to 0.0001% by weight, preferably 0.01 to 0.001% by weight. When the acid catalyst is used as such a low concentration aqueous solution, a large amount of water is entrained in the reaction system, and as a result, the reaction rate of the condensation reaction which is a competitive reaction can be suppressed. Therefore, as a tendency, OH groups generated by hydrolysis disappear at an appropriate rate, and it becomes easy to obtain a reaction composition rich in a linear structure having a large amount of OH groups.

  The amount of the acid catalyst used is usually 0.001 to 10 millimoles, preferably 0 to the total amount of 100 moles of hydrolysable groups (typically alkoxy groups) of the hydrolyzable silane compound in the hydrophilic solvent solution. 0.1 to 10 millimoles.

  The aqueous acid catalyst solution is dropped continuously, but the dropping rate thereof is appropriately selected so that the temperature in the reaction system does not rapidly rise. The dropping rate of the aqueous acid catalyst solution is usually 1 to 10 ml / min, preferably 3 to 5 ml / min, per 100 ml of the hydrophilic solvent solution. The dropped catalyst aqueous solution is immediately uniformly diffused by stirring and uniform hydrolysis is performed. In addition, the stirring method can employ | adopt the method employ | adopted by the normal chemical reaction.

  The hydrolysis and condensation reactions of the hydrolyzable silane compounds are practically carried out sequentially and in parallel. From the viewpoint of obtaining a reaction composition rich in a straight chain structure having a large amount of OH groups, it is preferable to carry out the following three steps so that hydrolysis and condensation reactions are performed as much as possible. .

(1) Hydrolysis reaction process:
It is carried out by dropping an aqueous acid catalyst solution into a hydrophilic solvent solution under stirring conditions. The reaction temperature is usually 5 to 50 ° C, preferably 10 to 40 ° C. If the reaction temperature is below the above range, the hydrolysis reaction becomes too slow, and if it is above the above range, it is difficult to avoid the condensation reaction. Control of the reaction temperature is performed by the temperature and circulating amount of the refrigerant conducted to the jacket of the reactor, the dropping rate of the aqueous acid catalyst solution, and the like. When the boiling point of the hydrophilic solvent is low, the hydrolysis reaction is carried out under reflux conditions. The reaction time is usually 1 to 60 minutes, preferably 5 to 30 minutes.

  The hydrolysis reaction is an exothermic reaction, and the temperature of the reaction solution usually rises by 1 to 15 ° C. In order to confirm that the hydrolysis reaction is substantially complete, stirring is preferably continued until the reaction temperature falls by 5 to 10 ° C. after the completion of the dropwise addition of the aqueous acid catalyst solution.

(2) Condensation reaction process:
Following the above steps, the reaction temperature is raised if necessary, and the reaction is carried out under stirring conditions. The reaction temperature is generally 40-80 ° C, preferably 50-60 ° C. If the reaction temperature is lower than the above range, the condensation reaction becomes too slow, and if the above range is exceeded, it is difficult to avoid excessive condensation reaction. The heating rate is usually 0.1 to 10 ° C./min. The reaction time is usually 1 to 120 minutes, preferably 5 to 60 minutes.

(3) Condensation reaction termination step:
The reaction solution is cooled to stop the condensation reaction. The cooling temperature is usually 10 to 30 ° C. At this time, it is more effective to stop the condensation reaction by cooling dilution in which a hydrophilic solvent is added to reduce the concentration of the condensation reaction composition. The hydrophilic solvent is preferably the same as the reaction solvent, but another hydrophilic solvent may be used to adjust the liquid property.

  The amount of the hydrophilic solvent added is usually in the range of 50 to 150% by weight when it is expressed as the concentration of the hydrophilic solvent relative to the total amount of the hydrolyzable silane compound, the hydrophilic solvent subjected to the reaction and the aqueous acid catalyst.

  According to the above-described condensation reaction termination step by cold dilution, the storage stability of the resulting binder solution is enhanced, and it is possible to prepare a binder solution which can be adjusted to a concentration meeting the requirements of each application.

  The condensation reaction step described above determines the weight average molecular weight of the resulting reaction composition. The weight average molecular weight is usually 1000 to 5000, preferably 2000 to 4000. Such molecular weight corresponds to a multimer having a degree of polymerization n of 2 to 100.

  The above weight average molecular weight is a value measured by gel permeation chromatography (GPC) under the following conditions.

[Solvent] Tetrahydrofuran [Device Name] TOSOH HLC-8220GPC
[Column] TOSOH TSKgel Super HM-N (2) and HZ1000 (1) connected and used.
[Column temperature] 40 ° C
[Sample concentration] 0.01 mass%
[Flow rate] 0.6 ml / min
[Calibration curve] PEG (Use a calibration curve with a four-point cubic approximation with molecular weights of 20000, 4000, 1000, and 200.

  The binder solution for forming a silicon oxide thin film formed of the above-mentioned reaction composition is substantially transparent, and as a result of measurement using a kaolin turbidimeter, the turbidity is 10 or less.

[Silica fine particles]
The fine silica particles are not particularly limited, and spherical non-aggregated silica fine particles having an average particle size of 5 to 100 nm, hollow non-aggregated silica fine particles having an average particle size of 10 to 100 nm, and chain aggregates having an average primary particle size of 5 to 100 nm The silica particle etc. which consist of at least 1 type of silica particle etc. are mentioned. These are suitably selected according to the purpose of the silicon oxide thin film to be formed.

  Specific examples of the spherical non-aggregated silica fine particles include “Snowtex®-O”, “Snowtex®-O-40”, and “Snowtex®—manufactured by Nissan Chemical Industries, Ltd. OL "," Qutron (registered trademark) -PL-1 "," Qutron (registered trademark)-PL-3 "," Qutron (registered trademark)-PL-7 "and the like manufactured by Sakai Chemical Industry Co., Ltd. can be mentioned.

  Specific examples of the chain-like aggregated silica fine particles include “Snowtex®-OUP” (average length: 40 to 100 nm), “Snowtex®-UP” (average), manufactured by Nissan Chemical Industries, Ltd. Length: 40 to 100 nm), “Snowtex® PS-M” (average length: 80 to 150 nm), “Snowtex® PS-MO” (average length: 80 to 150 nm), “Snowtex® PS-S” (average length: 80-120 nm), “Snowtex® PS-SO” (average length: 80-120 nm), “IPA-ST-UP” (average length: 80-120 nm) Average length: 40 to 100 nm), “Fine Cataloid F-120” manufactured by Nippon Shokuhin Kasei Kogyo Co., Ltd., and the like.

  The coating liquid for forming a silicon oxide thin film is prepared to have an appropriate concentration in consideration of the coatability at the time of coating on a substrate, the film thickness and smoothness of a coating film, and the like. The concentration adjustment is performed by the addition of the above-mentioned hydrophilic solvent, but this concentration adjustment can be performed before or after mixing the silica fine particles.

  The present invention includes the following first to fourth steps.

  In the first step, the coating liquid for forming a silicon oxide thin film is coated on the surface of the plastic substrate wound in a roll shape while being drawn out.

  The plastic substrate may be a film (100 μm or less) or a thicker sheet. Incidentally, as the plastics, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyimide (PI), polymethyl methacrylate (PMMA), cycloolefin polymer (COP) and the like can be mentioned. The surface of the substrate may be surface-modified or non-treated.

  The application of the coating solution is not particularly limited as long as it can be carried out continuously, and mention may be made of a die coating method, a spray coating method, a gravure coating method, a roll coating method, a curtain coating method, a screen printing method and an inkjet printing method. it can.

  The applied film thickness is appropriately selected according to the purpose of the silicon oxide thin film to be formed. It is usually 50 to 5000 nm.

In the second step, the coating liquid on the surface of the plastic substrate carried out of the first step is dried.
The above drying is performed to remove the solvent, the drying temperature is usually 50 to 80 ° C., and a hot air drier or the like is suitably used. The drying time is usually 1 to 10 minutes, preferably 1 to 5 minutes.

In the third step, the coating solution on the surface of the plastic substrate carried out from the second step is irradiated with ultraviolet light to be cured to form a silicon oxide thin film.
The above curing treatment is performed mainly to bond the silanol group (Si-OH) contained in the binder liquid and the oxygen-containing functional group such as hydroxyl group or carboxyl group on the substrate surface, thereby forming a silicon oxide thin film Be done.

  The above curing treatment is performed by irradiating ultraviolet rays in the presence of oxygen. Ultraviolet light includes near ultraviolet light (near UV, wavelength 200 to 380 nm), far ultraviolet light (wavelength 10 to 200 nm) and extreme ultraviolet light (extreme UV, wavelength 1 to 10 nm), but usually far ultraviolet light is effective. Examples of the ultraviolet ray source include a low pressure mercury lamp, a high pressure mercury lamp, an excimer ultraviolet (excimer UV) lamp, a halide lamp, and a laser. The irradiation time of the ultraviolet light is usually 1 second to 3 minutes.

  In the case of the curing treatment performed by irradiating ultraviolet light in the presence of oxygen, a silicon oxide thin film with significantly improved substrate adhesion is formed. The reason is estimated as follows.

  That is, the surface of the plastic substrate is activated (modified) by active oxygen generated by the action of ultraviolet light, and the silanol group (Si-OH) contained in the binder liquid is strongly bonded to the surface of the substrate.

  In the present invention, since the heating process is not essential for the curing process, a large area and a short time of film formation are possible.

  In the fourth step, the silicon oxide thin film laminate carried out of the third step is wound into a roll and wound up. The winding is usually performed so that the silicon oxide thin film is located inside.

  FIG. 1 is a process schematic diagram omitting the details for carrying out the continuous manufacturing method of the present invention. In the figure, reference numerals (1), (3) and (4) are transport rollers constituting a film pass line, (2) and (5) are backup rolls, (6) is a coating solution supply pan, (7) ) Is a dryer, (8) is an ultraviolet irradiation device, (10) is a plastic substrate wound in a roll, (11) is a gravure roll, (12) is a doctor blade, and (20) is a silicon oxide thin film lamination It is a rolled body of the body.

<Roll-shaped roll of silicon oxide thin film laminate>
The roll-like wound body of the silicon oxide thin film laminate according to the present invention is a roll-like wound body of a silicon oxide thin film laminate composed of a base material film and a silicon oxide thin film formed on the surface thereof. Is characterized by having a porosity of 10% or more as a value calculated by the relational expression of the porosity and the refractive index by the Lorentz-Lorentz equation, and is manufactured, for example, according to the above-mentioned continuous manufacturing method.

  The silicon oxide thin film having a porosity of 10% or more exhibits a low refractive index, is usually in the range of 1.16 to 1.42, and is extremely excellent as a low reflection film. The upper limit of the porosity of the silicon oxide thin film is 65%, and the preferable range is 20 to 50%.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples within the scope of the present invention.

Example 1
Preparation of Binder Liquid for Forming Silicon Oxide Thin Film
(1) Hydrolysis reaction process:
In a 2 L jacketed reactor, 50 parts by mass of product "KBM22" (content of 99% by weight of dimethyl methoxysilane) manufactured by Shin-Etsu Silicone Co., Ltd. Product "silicate MS51" manufactured by Mitsubishi Chemical Corporation (average degree of multimerization n: 7, methyl silicate 200 parts by mass of oligomer content 99.8% by weight) and 500 parts by mass of ethanol are charged, the reaction upper limit temperature is set to 40 ° C., 330 parts by mass of 0.007% by weight aqueous hydrochloric acid solution is dropped over 10 minutes under stirring conditions did. At this time, the reaction temperature rose by 5 to 10 ° C. due to the exothermic reaction. Stirring was continued until the reaction temperature dropped 5 to 10 ° C. The proportion of the multimer in the bifunctional hydrolyzable silane compound (the proportion of the silicate MS51 to the total amount of “KBM 22” and “silicate MS 51”) is 80% by weight.

(2) Condensation reaction process:
After the hydrochloric acid aqueous solution was dropped, the temperature was raised to 60 ° C. over 30 minutes under stirring conditions, and held at 60 ° C. for 30 minutes. Then, it cooled to room temperature.

(3) Condensation reaction termination step:
After cooling, 1,100 parts by mass of ethanol were mixed and stirred for 30 minutes to obtain 2,180 parts by mass of an alkoxysilane composition (A).

<Preparation of coating liquid for forming silicon oxide thin film>
12000 mass parts of ethanol was added to 2180 mass parts of the alkoxysilane composition (A) obtained above, and the alkoxysilane composition (B) 14180 was obtained by stirring for 30 minutes.

  2040 parts by mass of spherical non-aggregated silica (product "Snowtex O" manufactured by Nissan Chemical Industries, Ltd.) is added to 14180 parts by mass of the alkoxysilane composition (B) obtained above, and stirred for 30 minutes to obtain a silicon oxide thin film A forming coating solution was obtained.

<Continuous production of roll-like wound body of silicon oxide thin film laminate>
The following first to fifth steps were carried out by the same method as shown in the process conceptual diagram of FIG.

(Step 1)
As a plastic substrate (10) wound in a roll shape, a 3.5 μm thick polyethylene terephthalate (PET) film roll (width 780 mm, length 200 m) is used, and the PET film is easily formed by a gravure coater while pulling this out. The adhesive untreated surface was coated with a coating solution for forming a silicon oxide thin film.

(Step 2)
As a drier (7), a tunnel drier with a furnace length of 20 m was used. It dried on the conditions of drying temperature 70 degreeC, and residence time 2 minutes.

(Third step)
A high pressure mercury lamp (manufactured by Panasonic Corporation) was used as the ultraviolet irradiation device (8). Under the conditions of the illumination of 590 mW / cm ² , the integrated light quantity of 490 mJ / cm ² and the line speed of 10 m / min, the ultraviolet rays were irradiated under the atmosphere. The thickness of the silicon oxide thin film stack was 100 nm.

(Step 4)
A roll-like wound body (20) of a silicon oxide thin film laminate having a width of 780 mm and a length of 200 m was obtained with the silicon oxide thin film positioned inside.

[Adhesiveness test method]
According to JIS K5600, an adhesion test was conducted by a cross-cut method using an industrial 24 mm cello tape (registered trademark) manufactured by Nichiban Co., Ltd. as an adhesion tape, and adhesion was evaluated.
That is, after forming 25 grids of 5 mm intervals with a cutter knife, cellophane tape was attached to the membrane surface and pulled apart, the number of remaining membranes without peeling was counted and evaluated.
In addition, since the silicon oxide thin film has a property close to vitreous, a crack is easily generated when forming a grid with a cutter knife, and an accurate adhesion test becomes difficult. Therefore, the grid distance of JIS K5600 is Although it is 1 mm or 2 mm, the grid spacing is changed to 5 mm.
The ratio of the number of non-peeling squares to the total number (25) of squares (film remaining rate) was determined. The results are shown in Table 1.

[Damp-heat resistance test]
The silicon oxide thin film laminated PET prepared in the example and the comparative example is held for 30 minutes in an environmental tester (SH-641 manufactured by ESPEC) set to an environment of a temperature of 60 ° C. and a relative humidity of 95%. went. The state of decreased adhesion was evaluated by the above-mentioned adhesion test method. The results are shown in Table 1.

Comparative Example 1:
A silicon oxide thin film laminated PET was produced in the same manner as in Example 1 except that no ultraviolet light was irradiated. The results are shown in Table 1.

Comparative example 2:
Removal of the solvent was carried out at 120 ° C. for 10 minutes, and a silicon oxide thin film laminated PET was produced in the same manner as in Example 1 except that the ultraviolet light was not irradiated. The results are shown in Table 1.

1, 3, 4: Transport roller 2, 5: Backup roll 6: Coating liquid supply pan 7: Dryer 8: UV irradiation device 10: Plastic substrate 11: Gravure roll 12: Doctor blade 20: Silicon oxide thin film laminate Roll winding body

Claims (4)

  A roll-like wound body of a silicon oxide thin film laminate comprising a base film and a silicon oxide thin film formed on the surface, wherein the porosity of the silicon oxide thin film is the relation between the porosity and the refractive index according to Lorentz-Lorentz equation The roll-like wound body of a silicon oxide thin film laminate characterized in that it has a value of 10% or more calculated by the formula.   The roll-like wound body of a silicon oxide thin film laminate according to claim 1, wherein the refractive index of the porous silicon oxide thin film is 1.16 to 1.42.   A coating liquid for forming a silicon oxide thin film is prepared which contains a binder liquid comprising a reaction composition obtained by hydrolyzing and condensing a hydrolyzable silane compound and silica fine particles, and the plastic group wound in a roll shape The first step of coating the coating liquid for forming silicon oxide thin film on the surface while pulling out the material, the second step of drying the coating film on the surface of the plastic substrate carried out from the first step, and carried out from the second step The coating film on the surface of the plastic substrate is irradiated with ultraviolet light and cured to form a third step of forming a silicon oxide thin film, and the silicon oxide thin film laminate carried out from the third step is wound into a roll and wound. A method for continuously producing a roll of silicon oxide thin film laminate, comprising the steps of: The continuous manufacturing method according to claim 3, wherein the coating solution on the surface of the plastic substrate is irradiated with ultraviolet light in the presence of oxygen.

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